National Aeronautics and Space Administration

Ionic Liquid Facilitated Recovery of Metals and Oxygen from Regolith

Eric T. Fox, Laurel J. Karr, Peter A. Curreri, Gary S. Thornton, Kevin E. Depew, John M.

Vankeuren, Matthew Regelman, NASA/MSFCMatthew J. Marone, Mercer UniversityDavid N. Donovan, Qualis Corporation

Mark S. Paley, AZ Technology

September 18, 2018

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https://ntrs.nasa.gov/search.jsp?R=20180006404 2020-08-07T09:31:16+00:00Z

What does Regolith Offer?• In-space manufacturing is a promising route to

reduce the launch mass of deep space explorationmissions.

• However, these processes still require feedstock.• Producing these feedstocks from in situ resources

(in situ resource utilization or ISRU) furtherreduces the mass launch required for thesemissions

• Martian and lunar regolith contain valuableelements for many applications such as:

• Fe and Mg for aerospace applications• Si for solar cells• Na or Mg for the preparation of binders for

cement like materials• Oxygen for life support or propellant

• However, rather than being found in theirelemental form, these materials are found in highlystable oxides.

• Processing these oxides to recover high puritymaterials is technically challenging.

Oxide Processing Techniques• Terrestrial mining technology to recover metals from metals oxides is very mature.• Processes generally use large volumes of chemicals which are often caustic or corrosive

or thermal methods which require high energy inputs.

• NASA has studied molten oxide electrolysis (MOE) as a potentially space suitable approach to recovering metals from metal oxides.

• MOE works, but requires high temperatures (1400 – 2000 °C), so energy inputs are high. Additionally, these high temperatures impose significant material compatibility limitations.

MOE furnace during plating.

What are Ionic Liquids?• Ionic liquids (IL) are organic salts which are molten at or near room temperature.• Being entirely composed of ions, ILs have a number of properties that make them attractive

for in-space use, including high electrochemical and thermal stability, low vapor pressure,and high ionic conductivity.

• The chemical structure of ILs can be readily modified through simple chemical processes,which allows for the preparation of task specific ILs, or ILs with properties tuned for a givenapplication.

• ILs are potentially useful in a number of NASA relevant applications, includingenvironmental control and life support, advanced manufacturing, in situ resource utilization,and propulsion.

• Select ILs have been shown to chemical digest many metal oxides.

M.D. Joshi and J. L. Anderson RSC Adv., 2, 5470–5484 (2012).Table salt (left) and an IL (right).

The Process• A three step process that uses ILs to digest regolith and recover high purity metals has

been demonstrated.• First, an acidic IL is used to digest the metal oxide producing a solution of dissolved metal

in depleted IL and water as a byproduct.

• The water produced in the first step is electrolyzed and the H2 produced is stored for use inthe third step.

• The dissolved metals are electrochemically plated out of solution while the depleted IL isregenerated to its acidic state.

• The IL is then ready for reuse to digest additional regolith.

2HSO4- + MO → 2SO4

2- + M2++ H2O

M2++ 2e- → M ‖ 2SO42- + H2 → 2HSO4

- + 2e-

Regolith Digestion Water Electrolysis Metals Plating and IL Regeneration

Digestion of Metal Oxides

• There are many “acidic” ILs available.• 1-ethyl-3-methylimidazolium hydrogensulfate (EMI HSO4)

was the primary IL used for this work.• Offers a good balance of fluidity, electrochemical stability,

chemical reactivity, and vapor pressure.• EMI HSO4 has successfully digested Fe and Mg oxides, as

well as Ni metal.• Other ILs have been identified to partially digest feldspar

and to fully digest TiO2 at 200 °C.• No ILs have been able to completely digest SiO2 and no

work has been performed with CaO.

EMI HSO4

Solution of EMI HSO4 and 0.1 M Copper (left), nickel (middle), and magnesium.

Metals Electroplating

Oxidant Reductant Eo(V) vs. SHENi2+ + 2e- ↔ Ni -0.25Fe2+ + 2e- ↔ Fe -0.44Ti2+ + 2e- ↔ Ti -1.63Al3+ + 3e- ↔ Al -1.662

Mg2+ + 2e- ↔ Mg -2.372Ca2+ + 2e- ↔ Ca -2.868

Table of Standard Electrochemical Potentials for Regolith Processing

Incr

easin

g El

ectr

opos

itivi

tyLimit of aqueous solutions

• Sequential application of increasing reduction potential allows for the recovery of singleelements from the solution.

• Recovering N elements would require N + 1 electrodes, where the extra electrode wouldbe used to plate out all dissolved species that were less electropositive than the targetedmetal.

• Aqueous mineral acids solutions only allow for the recovery of Fe and Ni, as water beginsto electrolyze at -1.23 V.

• The large electrochemical windows of ILs allow for the recovery of highly electropositiveelements such as Mg.

• pH measurement of the plating solutions show a change from 4, representing the depletedIL solution, to 2, indicating that the IL is fully regenerated.

Recovery of Single Metals

Ni2+

Fe2+

• 0.05 M solution of metal in IL• 93% Fe, 7% Ni (m/m)• Typical of a Ni-Fe meteorite• Ni reduces around -0.8 V and Fe

reduces around -1.0 V• Peak assignments were verified

by single element CV

Recovery of Single Metals

SEM micrograph and SEM EDS analysis of electroplated metals. Water recovered from IL after digestion of Asteroid Vesta material.

• Electroplating of Fe-Ni solutions resulted in the recovery of single elements with puritygreater than 99%.

• The water byproduct from the metal oxide digestion was successfully recovered throughvacuum distillation.

Engineering Development Unit

• An Engineering Development Unit was fabricated to allow for the refinement of the designof flight hardware for experiments in microgravity.

• Contains three electrodes to recover Ni and Fe.• Fully isolatable anolyte chamber prevents regenerated IL from digested plated material• Work is ongoing to refine the fully autonomous control systems and electrochemical

regime.

Bulk Electroplating

Glassy carbon electrode at t = 0 min

• Electrolyte was a solution of 0.1 M EMI HSO4 and 0.05 M metal (93% Fe, 7% Ni) in water.• Initial testing at -0.95 V targeting Ni recovery resulted in no current and the lack of metal

deposition was confirmed by SEM EDS.• Increasing the applied reduction potential to -1.3 V produced a small current of 1 mA.

E = -1.3 V vs. Pt pseudoreference

Bulk Electroplating

Glassy carbon electrode at t = 25 min

• At approximately 20 min, the measured current started a rapid increase.• This corresponded to the appearance of metal deposits on the surface of the electrode.

E = -1.3 V vs. Pt pseudoreference

Bulk Electroplating

Glassy carbon electrode at t = 35 min

• The electrode was almost entirely covered with deposited metal.• The fluctuations in current are the result of metal flakes forming and detaching from the

electrode resulting significant surface area changes.• Bubbles are from the hydrolysis of water

E = -1.3 V vs. Pt pseudoreference

Bulk Electroplating

Glassy carbon electrode at t = 55 min

E = -1.3 V vs. Pt pseudoreference

• The electrode surface area was entirely covered with deposited metal.

Bulk Electroplating

Glassy carbon electrode at t = 375 min

• The experiment was terminated after approximately 6 hours of runtime due to anincreasingly rapid temperature rise. This was the result of the exothermic absorption of H2onto the Pt black anode and resistive heating of the electrolyte.

• Analysis of the total charge suggests half of the dissolved material was recovered.

E = -1.3 V vs. Pt pseudoreference

T = 33 °C

Bulk Electroplating

• SEM EDS indicated that the deposited metal had an identical composition as the originaldissolved metals.

Summary

• An IL-based process that allows for the digestion of regolith and recovery of metals andoxygen has been demonstrated.

• The process is 100% closed loop in regards to chemical reagents, requiring only energyand regolith inputs.

• High purity metals have been recovered from binary solutions.• ILs have been identified to chemically process the majority of the metal oxides found in

martian and lunar regolith.• The development of hardware for an eventual flight experiment is ongoing.• Further refinement of the electrochemical regime and hardware is required.